Process for the preparation of soluble heavy-metal compounds of thio-protein bodies.



if a suitable quantity of copper has entered i and shaken up energetically for some time.

Gentle warming is advantageous, preferably at a temperature at which no appreciable decomposition of the protein is produced. If thc reaction is 'complete the product ma be used for preparin the copper compoun In order to test if t e reaction is complete a portion of the reaction' product is treated with an ammoniacal solution of copper sulfate, whereupon a clear change should oef cur in the color of the metallic compound. A precipitant, forv example, 4ether-alcohol or acetone is then added, and the precipitate is, if necessary, analyzed after being washed with water for the purpose of ascertaining the product. After having ascertained from a portion of the sulfur compound that a suitable quantity of copper may combine with itI prepare the copper compound in lthe following way: Iinix the sulfur compound prepared in the described way with 8 grams of ammoniacal copper acetate dissolved in, for instance 120 cc.' of Water. The copper compoundI is then precipitated with 150 cc. of acetone. The product can be redissolved in alkali, for instance with l*100 cc.v

of 1% :caustic potash solution, then re- .precipitated with -an organic precipitant for example alcohol-ether, and finally Washed until the alkaline reaction has disappeared the excess of the reagents being also reinoved at the same time. The resulting copper compound contains about 20%of copper and 12% of sulfur.

Analysis.

0.2114 gm. gave 0.0548 gm. cao-20.71% cu. 0.2270 0.0583 20.47% 0.1901 0.1503 Bso.=11.05%s.

In the' preparation of the peptone-silver compounds, a solution of silver chlorid in ammonia is used, about 8 grms. of silver chlorid dissolved in 100 cc. of ammonia (sp. gr. 0.9), being taken for use with the sulfurized stock solution. In other respects the procedure is the same. The silver compound contains about 41% of silver and 6% of y sulfur.

Aaah/aia.

0.3036 grin. gave 0.1669 gmx. AgCl :41.37% Ag. 0.4372 0.2390 :41.11% 0.2309` 0.0902 luS04= {LW/0S.

ing the alkaline solution ofthe thio-peptone compound in intimate contact with metallic mercury. The sulfurized stock solutlon 1s metallic mercury in a shaking apparatus runnmg at 100 revolutions per minute. The

lliquid is then separated from. the unabsorbed mercury and' treated as above. The

mercury compound contains` about 38% of mercury and' 6.5% ofv sulfur.

Analysis.

0.2436 grm. gave 0.1070 fm1. H S==37J H 0.2409 0.1080 E y 38.6573 g 0.3164 0.1602 BaSO4== 6.52%8.

In the preparation of peptone-iron compounds powdered metallic iron is allowed -agitated for 3 days along with 10 grins. of y to act on the alkaline solutions of the thioprotein compounds; or pre-cepitated colloidal ferr-ic hydroxid In'ayA also be used.

The sulfurized stock solution is agitated .i

in a shaking apparatus along with 10 grms. of powdered metallic iron until the-,solution has 'acquired a deep green color, which occurs in about l to 2 hours. The liquid is separated from the undissolved metal, and the green ferro-compound is preci itated from the liquid, as above. 'The sul rizedy stock solution may also be mixed with 8 grins. of precipitated :collodial ferrie by? in 50 cc. of a 5% solution of caustic soda',-

and after being filtered,a the solution is placed in a high cylinder, into which a current ot' carbon oxysulfidV is passed slowly for 3 4- hours in the warm' (about 309-40o 0.),

untilv the solution has turned golden yellow in color. 'l`l1etemperature should again be maintained at such a level that no extensive'decomposition of the proteids can occur.

In the preparation of the copper compound, use is made for example, of ammoniacal copper acetate, 8 grms. of which dissolved in about 120 grms. of water being taken for use with a stock solution prepared and sulfurizcd as above. The ammoniacal copper acetate is poured slowly-within a few minutesinto the stock solution of thio-protein, with continued stirring, the temperature being kept at 15-20o C. The solution, which is orange colored at first becomes darker and darker until at last a clear, deep brown solution is obtained. After leaving it to .stand for about 15 minutes, an equal volume -for the most part separate out in ilocculentform. After filtration through a cloth filter.

they are repeatedly nutshellji'itb,v atone of incassa strength, and nally with absolute alcohol and ether. After pressing, the product is dried` at room temperature and powdered. The yield (9 grms.) can, it is truc be increased by increasing -the amount o precipitant used; but in such case the prodi uct willbe less pure. lt ought "to dissolve without residue, in the proportion. 1:5, in water which is just yalkaline to litmus {one drop of caustic soda); and if such be not the case it must be dissolved in 1:10 caustic soda solution of 0.5% strength and reprecipitated,

To obtain an analogous silver compound, a solution of silver chlorid in, ammonia is used; While Jfor preparing a corresponding Analysis. cecco gm. gave 0.1027 gm. caw-212cm', ou. 0.3184 0.1076 ='Z7.()0% Emomple [IIs-A stocli solution is prepared consistingl of 5 farms. of casein dissolved in 100 cc. of u. 57% solution of caustic soda, and treated with 2 cc. of carbon disulid. The mixture is gently warmed and shaken, the reaction taking 3 days. rThe surplus carbon disullid ispreferably eirnelled by heating over the Water bath. The completion of the reaction is ascertained in the same manner as described in Example l.

In the preparation of the copper compound the cooled golden yellow solution is treated with about l grins. oi copper acetate dissolved in 60 cc. of ammonia (0.9% strength), and the clear brown solution is precipitated with either acetone or alcoholether and Washed, the dissolving and precipitation being repeated. The compound contains about 18% of copper.

Analysis.

i 0.2904 grin; gave 0.04551 grin. Cu0=`l7.9l% Cuv Ezcrwtple [Vfstock solution is prepared, consisting;r of 130 cc. of horse serum albumin carefully mixed with grins. of powdered sodium liydroxid over the Water bath until complete solution is effected. This done, 5 cc. of carbon disulid are added, and the procedure of Example lli is followed. The compound contains 1257/'21 Cu.

Anali/cis.

0.35m grin. gave 0.057 grm. 0102121162, Cu.

ln the solid state the new cupro-com pounds are darli' brown. T he copper is not thrown down from the solutions by sulfurei'ed hydrogen. The compounds are solublein alkalis but are not dissolved by acids these 'latter in fact precipitating them in the colloidal state but not decomposing them except at high temperatures. The peptonecopper compounds are also soluble in Water.

The silver compounds are dark brown to lack in color, are soluble in alkalis, and are not thrown down from the solutions by sulfureted hydrogen. They are, insoluble in acids, are precipitated in the colloidal state by acids, and are decomposed by the latter at high temperatures only. No silver chlorid is precipitated by addingr sodium'chlorid. The silver thio-peptone compounds are soluble in Water.

The mercurycompoundsaee deep black. They are soluble in alkalis, are precipitated in the colloidal form by acids, and are decomposed by the latter only at high teinperatures: The .peptone compounds are soluble in Water, and the mercury is not precipitated by sulfureted hydrogen.

The ferri compounds are reddish, and the ferro compounds greenish in color..

The compounds are very completelynnd quickly absorbed by the human organism;

and they can be employed in either the dissolved or undissolved condition. For eX- ample, the casein compounds can be applied to the skin in the undissolved condition.

The solutions ofthe thio-peptone heavy metal compounds are particularly valuable, being very readily soluble in Water to form a perfectly neutral solution. ln this Way it is possible to employ the metals inl the] form of a highly concentrated solution.

The compounds have no corrosive action, and therefore do not irritate the tissues. They are also tasteless, on which account the iron compounds are specially suitable for nutrient purposes. The compounds have a powerful bactericidal eiect.

l. Thel process of obtainingr soluble heavy metal compounds of thio-protein bodies, consisting in rst dissolving proteid substances in media possessing an alkaline reaction, then converting said proteid substances into thio-protein bodies by the action of a sulfuncarbon compound, and subsequently treating the tino-protein bodies while in alkaline solution with reagents, which Will produce heavy metal compounds rvof same which are soluble in Water and in treating the reaction product with an am,- l

moniacal solution of copper sulfate the. resulting compounds being thrown down from the -solution by acetone. 5 3. The process for 'obtaining soluble copper compounds of thioprotein bodies, consisting in'first diesolvinf,r a proteid substance in a solution. of caustic soda, filter-y billed dition of alkalis, common` salt or blood serum and being precipitated from its aqueous solution on addition of ether-alcohol, acetone and acids.

A compound, comprising copper comfl with a thioprotein-body, having brown to brownish dark color, soluble in water and alkalis, not precipitated from its solution on addition of alkalis, commonl salt f and blood-serum, being preclpitate-d from its aqueous solution on addition of ether-alcohol, acetone and acids.- y

ln testimonywhereof; I have signed my name to this specification inthe presence -of two subscribing' Witnesses.-

ROBERT UHL( l'Vitnesses:

TENGEN MAX ROTH, A. W. CORTE. 

